CN109200978A - Handle the method and system of chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water - Google Patents
Handle the method and system of chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water Download PDFInfo
- Publication number
- CN109200978A CN109200978A CN201810172039.XA CN201810172039A CN109200978A CN 109200978 A CN109200978 A CN 109200978A CN 201810172039 A CN201810172039 A CN 201810172039A CN 109200978 A CN109200978 A CN 109200978A
- Authority
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- China
- Prior art keywords
- hydrolysis
- water
- reactor
- dead catalyst
- strong brine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 166
- 239000002351 wastewater Substances 0.000 title claims abstract description 71
- 239000000460 chlorine Substances 0.000 title claims abstract description 64
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 63
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000004411 aluminium Substances 0.000 title claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 42
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 159
- 239000012267 brine Substances 0.000 claims abstract description 149
- 230000007062 hydrolysis Effects 0.000 claims abstract description 149
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 149
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 109
- 239000007788 liquid Substances 0.000 claims abstract description 96
- 239000002253 acid Substances 0.000 claims abstract description 74
- 239000002893 slag Substances 0.000 claims abstract description 59
- 239000007787 solid Substances 0.000 claims abstract description 57
- 238000004062 sedimentation Methods 0.000 claims abstract description 55
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 52
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 22
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 196
- 238000003860 storage Methods 0.000 claims description 80
- 239000004744 fabric Substances 0.000 claims description 67
- 238000005189 flocculation Methods 0.000 claims description 65
- 230000016615 flocculation Effects 0.000 claims description 64
- 230000018044 dehydration Effects 0.000 claims description 50
- 238000006297 dehydration reaction Methods 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 50
- 238000012856 packing Methods 0.000 claims description 47
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- 230000008021 deposition Effects 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- -1 polyethylene Polymers 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 238000007791 dehumidification Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000003921 oil Substances 0.000 description 120
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 118
- 235000011121 sodium hydroxide Nutrition 0.000 description 57
- 230000008569 process Effects 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000012546 transfer Methods 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 239000003344 environmental pollutant Substances 0.000 description 13
- 231100000719 pollutant Toxicity 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 229920002313 fluoropolymer Polymers 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000013067 intermediate product Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 230000005484 gravity Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000013329 compounding Methods 0.000 description 8
- 239000008394 flocculating agent Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 241001282153 Scopelogadus mizolepis Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J19/1862—Stationary reactors having moving elements inside placed in series
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- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C02F11/16—Treatment of sludge; Devices therefor by de-watering, drying or thickening using drying or composting beds
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2001/007—Processes including a sedimentation step
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The present invention provides a kind of method and system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water.Hydrolysis is carried out this method comprises: 1) mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, until the residual activity of dead catalyst completely eliminates, obtains acidic hydrolysis liquid and the molten oil of acid;2) acidic hydrolysis liquid is mixed with the lye comprising alkaline waste water and carries out neutralization reaction, until reaction system is alkalescent, obtain the neutralizer containing metal hydroxides wadding body;3) neutralizer and flocculant are sufficiently mixed and are implemented sedimentation separation, the strong brine for collecting upper layer is back to hydrolysis, while collecting the concentration wadding body of lower layer;4) concentration wadding body is carried out dehydrating, collects wet solid slag, and the strong brine of abjection is back to hydrolysis;5) wet solid slag is dried, obtains desiccation solid slag.The above method can leniently eliminate the activity of dead catalyst, and the stability of technological operation and safety are good, and the quality for recycling oil product is high.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of processing chlorine aluminium acidic ionic liquids dead catalyst and
The method and system of alkaline waste water.
Background technique
Enter the acceleration propulsion phase as national clear gusoline upgrades strategy, it is high as ideal clean gasoline blend component
The demand of octane number alkylate oil has welcome the growth of explosion type.It is the master for producing alkylate oil by catalytic material alkylation of C4
Technique is wanted, existing alkylation process mostly uses greatly two conventional processing routes of hydrogen fluoride and sulfuric acid process.However, above-mentioned tradition
Process route, as catalyst, it is hidden not only to cause huge safety to technique, equipment and personnel using hydrofluoric acid and sulfuric acid
Suffer from, a large amount of " acid sludges " and great environment hidden danger is also constituted containing alkali waste water that furthermore technical process is discharged.Even if being thrown with height
Enter and regeneration treatment, flue gas SO are carried out to " acid sludge "2、NOxEnvironmental protection standard can not be met with sulphuric acid mist content.Therefore, alkylate oil
Production be badly in need of the advanced technologies of safer environmental protection.
Using ionic liquid as the catalyst of alkylated reaction, in product transformation efficiency, process safety and environment friend
To be much better than traditional hydrogen fluoride and sulfuric acid process in good property.Compared with hydrogen fluoride and sulfuric acid process, chlorine aluminium acidic ionic liquids
Alkylation process whole competitiveness is stronger, and the alkylate oil process units created at present uses.However, chlorine aluminic acid class
Ionic liquid allcylation technique still can generate a small amount of dead catalyst and alkaline waste water (i.e. alkali-wash waste water), wherein alkyl per ton
Carburetion by-product dead catalyst 3kg or so, alkali-wash waste water 20-30kg, yield are respectively the 5% and 3% of sulfuric acid process.Chlorine aluminic acid class from
The component of dead catalyst and raw catelyst that sub- liquefied alkyl technique generates is essentially identical, and only activity slightly reduces, and
Containing acid-soluble hydrocarbon, therefore there are the characteristics such as high activity, peracidity and high oil-containing, innoxious and disposal of resources is carried out to it
It is extremely necessary.
The patent of invention of 105457973 A of Publication No. CN discloses a kind of pair of chlorine aluminium acidic ionic liquids dead catalyst
The method and system handled, first clear up by dead catalyst and aqueous slkali-neutralization reaction is to eliminate dead catalyst
Activity with it is acid, then again in dead catalyst metal and oils resource recycle.The above method and system can be
Harmless treatment is carried out to chlorine aluminium acidic ionic liquids dead catalyst to a certain extent and realizes that Metals from Spent Catalysts and acid are molten
The recycling of oil, however the present inventor has found through numerous studies, there are still following defects for the above method and system: 1) anti-in resolution
Answering in device directly adds alkali clear up-neutralize to dead catalyst, and reaction process is very violent, the stability and peace of technique and system
Full property is relatively poor;2) the molten oil of acid in dead catalyst easily causes carbonization, the recycling of the molten oil of acid during resolution-neutralization reaction
Rate is lower than 70%, and the moisture content for the molten oil of acid that furthermore recycling obtains is high (moisture content is 7wt% or so), and that there are granulated carbons is miscellaneous
Matter (content of particle carbon impurity is 5wt% or so), the inferior quality of oil product;3) dead catalyst clear up-neutralize obtaining
The three-phase mixture being made of the molten oily phase/wadding body of water phase/acid, need to carry out demulsification receipts to oil emulsion in the molten oil of recovery acid
Oil is unfavorable for subsequent processing;4) metal and the molten oil of acid in dead catalyst, work are recycled using flocculation and twice dehydration mode twice
Skill is relative complex, and operating cost is higher.
In addition, carrying out alkali cleaning to alkylate oil product is to ensure oil quality in the technique of chlorine aluminic acid class ionic liquid allcylation
The important measures of amount usually contain sodium hydroxide, sodium metaaluminate, sodium chloride and a small amount of petroleum in the alkali-wash waste water discharged
Pollutant.It is handled currently, the alkali-wash waste water is usually discharged to sewage disposal system, not only needs to add a large amount of external source
Acids neutralizes it, and can increase a large amount of aluminium hydroxide materialized mud newly after neutralizing, the salt load of waste water after neutralization
It is higher with organic loading, serious impact is constituted to the stable operation of sewage disposal system.
It is useless for dead catalyst and alkali cleaning since chlorine aluminic acid class ionic liquid allcylation is the new process of petrochemical industry
The processing mode of these two types of novel pollution sources of water is still among continuous explore.Therefore, how useless to chlorine aluminium acidic ionic liquids
Catalyst and alkali-wash waste water these two types pollution sources carry out innoxious, recycling processing and utilization, thus realize chlorine aluminic acid class from
The green upgrading of sub- liquefied alkyl technique, is the significant problem that petrochemical industry faces.
Summary of the invention
The present invention provides a kind of method and system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, the party
Method and system can overcome the problems of the above-mentioned prior art, can not only leniently eliminate the activity of dead catalyst, technique
The stability of operation and safety are good, and furthermore the molten oil of acid in dead catalyst is not easy to be carbonized, and the rate of recovery of the molten oil of acid is high, recycle
The content of the molten W/O of acid and impurity that arrive is low, and the quality of oil product is high.
The present invention provides a kind of method for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, including walks as follows
It is rapid:
1) chlorine aluminium acidic ionic liquids dead catalyst is mixed with strong brine and carries out hydrolysis, until chlorine aluminic acid class ionic liquid
The residual activity of body dead catalyst completely eliminates, and separates to hydrolysis product, respectively obtains acidic hydrolysis liquid and acid is molten
Oil;
2) the acidic hydrolysis liquid is mixed with the lye comprising alkaline waste water and carries out neutralization reaction, until reaction system is weak
Alkalinity obtains the neutralizer containing metal hydroxides wadding body;
3) neutralizer and flocculant are sufficiently mixed and are implemented sedimentation separation, the strong brine for collecting upper layer is back to institute
Hydrolysis is stated, while collecting the concentration wadding body of lower layer;
4) the concentration wadding body is carried out dehydrating, collects wet solid slag, and the strong brine of abjection is back to the water
Solution reaction;
5) the wet solid slag is dried, obtains desiccation solid slag.
The present invention does not limit chlorine aluminium acidic ionic liquids dead catalyst (hereinafter referred to as dead catalyst) strictly, such as
It can come from the alkylated reaction using the ionic liquid-catalyzed C4 hydrocarbon of chlorine aluminic acid class, utilize the ionic liquid-catalyzed alkene of chlorine aluminic acid class
Polymerization reaction, catalysis Friedel-Crafts alkylated reaction or Friedel-Crafts acylation reaction generate useless catalysis
Agent.
In concrete scheme of the invention, chlorine aluminium acidic ionic liquids dead catalyst is to be urged using chlorine aluminium acidic ionic liquids
Change carbon four and produces the dead catalyst that alkylate oil generates;The viscosity of the chlorine aluminium acidic ionic liquids dead catalyst reaches 600-
800mPas, active component are mainly aluminium chloride, copper chloride etc., and other components are mainly acid-soluble hydrocarbon (i.e. sour molten oil).
The present inventor it has been investigated that, the above-mentioned prior art directly adds alkali clear up-neutralize will lead to dead catalyst
Reaction process is very violent, and reason may is that the main active component of chlorine aluminium acidic ionic liquids dead catalyst is chlorination
Aluminium, hydrolysis reaction is higher, can hydrolyze rapidly after contact with water and generate hydrogen chloride and make hydrolyzate in highly acid;Together
When, hydrolysis heat release increases Hydrolysis rate constant, further improves the hydrolysis reaction of aluminium chloride.Especially
It is that highly basic is directly added into aluminium chloride hydrolytic process, the neutralization reaction of highly basic and hydrogen chloride can discharge a large amount of heat, further
Increase the hydrolysis reaction of aluminium chloride;It cannot such as radiate in time, the heat release of momentary strong will form localized hyperthermia, to make
At the carbonization of the molten oil of acid and the generation of oil smoke, hydrogen chloride acid mist, the risk of explosion additionally, there may be.
Therefore, the present invention is before carrying out neutralization reaction to dead catalyst using lye, first by chlorine aluminium acidic ionic liquids
Dead catalyst is mixed with strong brine carries out hydrolysis;The study found that a large amount of strong brine is in the hydrolytic process of dead catalyst
The hot rapid dispersion that hydrolysis can be generated, so that the autoacceleration mechanism of hydrolysis be interrupted;Meanwhile it is high in strong brine
The chloride ion of concentration increases the concentration of hydrolysate, has certain inhibiting effect to hydrolysis.Aforesaid way can not only
Enough activity for leniently eliminating dead catalyst, while neutralization reaction heat can be eliminated to the facilitation of hydrolysis reaction, make
Technological operation is more stable and safe;In consideration of it, so as to complete the present invention.
In step 1) of the invention, hydrolysis is mainly used for the residual of chlorine aluminium acidic ionic liquids dead catalyst is living
Property completely eliminates;Specifically, when residual activity completely eliminates, the pH stable of acidic hydrolysis liquid is as hydrolyzed in 2.5-2.8
Reaction end.
In particular, the content of sodium chloride can be 15-22wt% in the strong brine in step 1);In addition, the chlorine aluminium
The input material volume ratio of acidic ionic liquids dead catalyst and strong brine can be 1:(50-60).
Research is found: the input material volume ratio of strong brine and dead catalyst is bigger, and the hydrolysis of dead catalyst is milder;When
When the input material volume ratio of strong brine and dead catalyst is lower than 50:1, the temperature rise of hydrolysis reaction system becomes obviously, and has hydrogen chloride
Acid mist evolution;When the volume ratio that feeds intake of strong brine and dead catalyst is lower than 10:1, starts the carbonization for the molten oil of acid occur and have oil
Cigarette generates.In view of strong brine and dead catalyst input material volume ratio it is excessive when required reactor volume it is excessive, therefore can will
The input material volume ratio of chlorine aluminium acidic ionic liquids dead catalyst and strong brine is set as 1:(50-60).
In addition, the mass content of sodium chloride is higher in strong brine, the hydrolysis of dead catalyst is milder;However, when dense
When the content of sodium chloride is higher than 22wt% in salt water, the excessive concentration of chloride ion in hydrolyzate can be made so as to cause sodium chloride crystallization
It is precipitated;When the content of sodium chloride in strong brine is lower than 15wt%, the temperature rise of hydrolysis reaction system becomes obvious.It therefore, can be with
15-22wt% is set by the content of sodium chloride in the strong brine.
Under the above conditions, the heating of entire hydrolysis reaction system is unobvious, and does not occur the molten oil carbon of acid and bright
Aobvious acid mist escapes phenomenon, and hydrolysis is more mild.
Further, the present inventor it has been investigated that, the prior art carries out clearing up-neutralization reaction using complete mixing flow reactor
The molten oil carbonization of acid be will lead to which the rate of recovery is lower, reason may is that the viscosity of dead catalyst is higher, in strong brine
In the form of drop occur, in the hydrolysis reaction of dead catalyst, the mass transfer between active component and moisture be control because
Element;Since hydrocarbon acid-soluble in dead catalyst is to the cladding of active component, so that the mass transfer between active component and moisture is weakened,
Its mild progress for being conducive to hydrolysis.However, if making between dead catalyst drop and water body with the progress of complete mixing flow state
Contact, can accelerate the separation of acid-soluble hydrocarbon and active component, and the mass transfer between active component and water body is reinforced, hydrolysis speed
Rate is enhanced, and hydrolysis reaction can more acutely;Meanwhile the molten oil of acid of generation can also be swept along into reaction system, both be held
Carbonization is easily caused, the rate of recovery of the molten oil of acid is furthermore reduced.
Therefore, the present invention carries out above-mentioned hydrolysis in plug flow packed bed reactor, to make hydrolysis more
Mildly (i.e. realization mild hydrolysis);At this point, dead catalyst is contacted with strong brine with flat-pushing stream mode, the back-mixing degree of material
Low, small to the disturbance of dead catalyst drop, the mass transfer between active component and moisture is weakened, and not only reduces hydrolysis
Intensity, and be conducive to the separation and recycling of the molten oil of acid.
Density in view of dead catalyst is about 1.36kg/L, and the density of acidic hydrolysis liquid and strong brine is about 1.2kg/L;This
When, sinking speed of the dead catalyst drop in strong brine is very fast, is unfavorable for the complete hydrolysis of dead catalyst.Therefore, of the invention
Structured packing is filled in plug flow packed bed reactor, which fully utilizes the high viscosity characteristic of dead catalyst, filling out
Crown_interception of the behavior of boundary layer and filler on material surface to catalyst;Since the viscosity of dead catalyst is high, inlet amount is small,
It is in membranaceous Laminar Flow on structured packing surface, and forms thicker laminar boundary layer, biggish stickiness power makes dead catalyst
The rate of settling be effectively controlled.Further, since the presence of inner layer of boundary layer laminar sublayer, the resistance to mass tranfer of storeroom increases, because
Mass-transfer efficiency between this dead catalyst and strong brine is also effectively controlled.Relative to random packing, the material stream of structured packing
Through-hole road is uniform, is less prone to channeling.
In particular, unobstructed flow path, and basic retaining layer can be provided by using high-throughput structured packing for strong brine
Stream mode, while the mass transfer between dead catalyst can be weakened.When reaction is hydrolyzed, dead catalyst is in the hole of structured packing
It being uniformly distributed in gap, the numerous elementary reaction environment of forming quantity, the strong brine of the big scale of construction and the time of contact of dead catalyst are long,
To ensure that the thorough hydrolysis to dead catalyst.
Research is found: the porosity and specific surface area of structured packing are affected to hydrolysis;Porosity it is too low or
When specific surface area is excessive, there is the risk of the molten oil of acid and impurity blocking filler duct;When porosity is excessively high or specific surface area is too small,
The crown_interception of dead catalyst is weakened, there are the incomplete risks of hydrolysis.The porosity of structured packing is in 0.95-
0.97m3/m3(i.e. every m3The pore volume of structured packing is 0.95-0.97m3), specific surface area is in 300-500m2/m3(i.e. every m3
The specific surface area of structured packing is 300-500m2) between when, the rate control of hydrolysis is preferable, neither easily causes duct stifled
Plug, while hydrolysis easily carries out completely.
Further, structured packing can be oleophobic property filler and can have inclined plate structure;The structured packing can also
Enough coarses promoted to the molten oil droplet of acid make bulky grain oil droplet be easier to float, to be conducive to the recycling of the molten oil of acid.
Specific structure and material to structured packing do not limit strictly;Structured packing for example can be Y type ripple orifice plate
The inclination angle of structured packing etc., ripple and axis can be 45 ° or so, so that the rejection effect to dead catalyst drop is good.This
Outside, the material of structured packing can be polyethylene (PE), polyvinyl chloride (PVC) or Kynoar (PVDF), with oleophobic
Property and acidproof resistance to chlorine corrosion, be conducive to the coarse of the molten oil of acid, consequently facilitating the molten oil of acid recycles.
Further, the air speed of above-mentioned plug flow packed bed reactor can be 0.25-0.5h-1.Wherein, when air speed is
0.5h-1When, dead catalyst is able to complete hydrolysis, and pH value can be stablized in 2.5-2.8;When air speed is 0.25h-1When, acidic hydrolysis
The oil content of liquid is minimum, and the molten oil of the acid recycled is at most.
The mild hydrolysis of dead catalyst and strong brine after the reaction was completed, the aluminium chloride isoreactivity component in dead catalyst is complete
Full inactivation, enters eventually into acidic hydrolysis liquid;The molten oil of acid in dead catalyst may be recovered through usual manners such as sedimentations
And it recycles.The sodium chloride content in acidic hydrolysis liquid that hydrolysis is formed is high, acidity is relatively strong and contains metal resource, subsequent
It can be neutralized to realize innoxious and recycling.
In step 2) of the invention, it can use alkaline waste water and the acidic hydrolysis liquid that hydrolysis is formed neutralized
Reaction;The present invention does not limit alkaline waste water strictly, such as can be that the ionic liquid-catalyzed carbon four of chlorine aluminic acid class is utilized to produce
The alkali-wash waste water that alkylate oil generates, sodium hydrate content are 10-15wt% or so.Aforesaid way is real by " treatment of wastes with processes of wastes against one another "
Show the synchronization combining processing to dead catalyst and alkaline waste water, both reduced the dosage of external source acid, alkali, while avoiding alkali
Wash impact of the waste water to sewage disposal system.
When underway and reaction, the concentration of lye is not limited strictly, concentration of lye can be according to chlorine in neutralizer
The concentration for changing sodium carries out being suitable for adjusting;It, can be with supplemented with exogenous alkali when alkaline waste water is insufficient for neutralization reaction necessary requirement
Liquid, alkaline waste water and external source alkalinity collectively form the lye that neutralization reaction is carried out to acidic hydrolysis liquid at this time.
Specifically, when the concentration of sodium chloride in neutralizer is lower than 15wt%, the concentration of lye can be increased;Work as neutralizer
When the concentration of middle sodium chloride is higher than 22wt%, the concentration of lye can be reduced.The compound concentration of external source lye is not limited strictly
It makes, the content of sodium hydroxide can be 25-35wt% in external source lye.
Among the above and in reaction process, hydroxyl in the metal ions such as aluminium, copper in acidic hydrolysis liquid and lye from
Son combines and forms metal hydroxides wadding body;Meanwhile the height that the sodium ion in lye and the chloride ion in acidic hydrolysis liquid are formed
The sodium chloride (i.e. strong brine) of concentration, a small amount of oils furthermore carried in acidic hydrolysis liquid are also transferred in neutralizer.
In the present invention, neutralization reaction can carry out in complete mixing flow reactor;Complete mixing flow reactor is able to carry out quickly
Neutralization reaction, so as to reduce the volume of reactor.In particular, the air speed of complete mixing flow reactor can be 1-2h-1;Its
In, when the air speed of complete mixing flow reactor reaches 2h-1When, acidic hydrolysis liquid complete neutralization, the pH stable of neutralizer is in 8.0-
8.5, as neutralization reaction terminal;When air speed increases to 1h-1When, the yield highest of the metal hydroxides wadding body in neutralizer,
The content of metal hydroxides wadding body reaches 2.5-3wt%.
The main composition of the neutralizer formed through above-mentioned neutralization reaction be metal hydroxides wadding body and strong brine, it is subsequent
Sedimentation separation is carried out using flocculant, initial gross separation can be carried out to metal hydroxides wadding body and strong brine.The dense salt collected
The hydrolysis for dead catalyst can be recycled in water;Volume reduces after metal hydroxides wadding body precipitation concentration, reduces subsequent
The load of dehydration.
In step 3) of the invention, flocculant is added into neutralizer, can be acted on by adsorption bridging, it will be loose
Little particle metal hydroxides wadding body is converted into closely knit bulky grain wadding body, is more advantageous to the precipitating of metal hydroxides wadding body.
The hybrid mode of neutralizer and flocculant is not limited strictly, such as can use pipe-line mixer and be sufficiently mixed, with
The sedimentation separation of wadding body and strong brine is carried out using flocculation deposition apparatus afterwards.
The present invention does not limit used flocculant strictly, such as can be flocculated using anion-polyacrylamide
Agent, more suitable for the flocculation of metal hydroxides wadding body.Specifically, the average molecular of anion-polyacrylamide flocculant
Amount may range from 600-1800 ten thousand, be further 1200-1800 ten thousand;Charge density may range from 10-40%, further for
10-30%.It can promote the phase between aluminium hydroxide, Kocide SD particle using above-mentioned anion-polyacrylamide flocculant
It mutually coheres, consequently facilitating forming bigger wadding body.
Further, research is found: when the above-mentioned flocculant of 20g or more being added in neutralizer per ton, the wadding body of formation
Coarse closely knit, settling property is good;When the additional amount of flocculant in neutralizer per ton is more than 30g, settling of floccus performance is mentioned
It rises less, and uneconomical in cost.Therefore, the dosage of above-mentioned flocculant can be set to neutralizer per ton and flocculation is added
Agent 20-30g.
In addition, when the sedimentation separation time reaching 2h, the boundary between wadding body and strong brine is concentrated when implementing sedimentation separation
Face is clear, and strong brine is carried secretly almost without wadding body, and concentration wadding body layer accounts for 25% or so of neutralizer volume;The sedimentation separation time is in 3h
When above, concentration wadding body layer precipitating is very thorough, only accounts for the 20% of neutralizer volume, and it is dense for reducing to continue growing the sedimentation time
Contracting wadding body layer volume is not contributed.Therefore, the time of sedimentation separation can be set to 2-3 hours.
After above-mentioned sedimentation separation, the content of strong brine is about 85-90wt%, metal hydroxide in the concentration wadding body of formation
The solid content of object is about 10-15wt%.In addition, a small amount of oil in neutralizer is concentrated in strong brine phase, therefore it is concentrated
The oil content of wadding body is very low, more cleans, and is convenient for its subsequent recycling.
In view of a large amount of strong brine is contained in concentration wadding body, absolute yield is larger, as metallurgical raw material or solid waste
Outward transport economy is poor, while strong brine is the required resource of dead catalyst hydrolysis.Therefore, the present invention to concentration wadding body into
Row dehydration to reduce the total amount of metal hydroxides system, while carrying out Returning utilization to strong brine.
In step 4) of the invention, the dehydration mode of concentration wadding body is not limited strictly, it can be using conventional
Mechanical dehydration mode, such as plate compression or centrifugal dehydration etc..Big, the contained water of the particle of metal hydroxides concentration wadding body
Based on Free water, no matter pressure filtration or centrifugal filtration mode is used, can be realized metal hydroxide solids and dense salt
The separation of water.Wherein, when being dehydrated using plate compression mode, operating pressure can be 0.45MPa or so;Using centrifugation side
When formula is dehydrated, the separation factor of centrifugal dehydration can be 3000 or so.The wet solid slag formed through above-mentioned dehydration is (i.e. golden
Belonging to hydroxide and wadding body be concentrated) moisture content is 60-70wt% or so;Dehydration separate the strong brine to be formed can be back to it is above-mentioned
Hydrolysis.
Further, the moisture in wet solid slag formed in view of dehydration is mainly capillary water, no matter uses sheet frame pressure
Filter or centrifugal dehydration mode are difficult to continue to reduce its moisture content and solid slag yield.It therefore, can in step 5) of the invention
Wet solid slag to be dried using thin layer drying or low temperature dehumidification drying mode, to be realized with lower energy consumption wet solid
The removal of capillary water in slag.
Thin layer drying technology has coupled conduction and radiant drying principle, generally uses hot fluid indirect heating manner, right
The vaporization rate of moisture is very fast in wet solid slag;Low temperature dehumidification dry technology is based on convective drying principle, general directly to be added using electricity
Hot mode, though the speed for dehumidifying of gasifying is slower than thin layer drying, however equipment investment is low, and technological operation is simple.There are waste heat Jie
In the case that matter can use, preferred coating dry technology.In addition, it is no matter dry using thin layer drying or low temperature dehumidification,
To reduce energy consumption by recycle-water latent heat of the steam;It is lighter in the pollution level for the condensed water that thermal energy recovery stage generates, it can
To be back to the preparation of lye and flocculant solution.The desiccation solid slag moisture content formed through above-mentioned drying process is 10-20wt%.
The method of processing chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water provided by the invention, it is main using " temperature
With hydrolysis-quickly neutralization-flocculation sedimentation-mechanical dehydration-removal moisture drying " agent technology route, which is easy to operate, can
The activity of dead catalyst is leniently eliminated, while avoiding impact of the alkaline waste water to sewage disposal system, integrated artistic operation
Stability and safety it is good, metal and oils resource in dead catalyst are effectively recycled and are utilized, intermediate product
It is recycled, process costs are relatively low, are conducive to the green upgrading for pushing ionic liquid allcylation technique.
The present invention also provides a kind of for implementing the system of the above method, including hydrolysis reactor, neutralization reactor, flocculation
Settling system, mechanical dehydration device and desiccation apparatus;
The hydrolysis reactor, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis;
The neutralization reactor is connect with the hydrolysis reactor, the acidic hydrolysis liquid for generating the hydrolysis
It is mixed with the lye comprising alkaline waste water and carries out neutralization reaction;
The flocculation sedimentation system is connect with the neutralization reactor, the neutralizer for generating the neutralization reaction with
Flocculant is sufficiently mixed and implements sedimentation separation;
The mechanical dehydration device is connect with the flocculation sedimentation system, for the concentration to being formed through the sedimentation separation
Wadding body is carried out dehydrating;
The desiccation apparatus is connect with the mechanical dehydration device, for the wet solid slag formed through the dehydration into
Row is dried.
Further, the hydrolysis reactor is plug flow packed bed reactor, in the plug flow packed bed reactor
In be filled with structured packing, the porosity of the structured packing is 0.95-0.97m3/m3, specific surface area 300-500m2/m3。
The present invention does not limit the specific structure of hydrolysis reactor strictly, can use the hydrolysis of this field routine
Device.In concrete scheme of the invention, hydrolysis reactor includes shell, is successively arranged ring from top to bottom on the top of the shell
Shape collection tank, the water distributor for being distributed strong brine and the distributing device for being distributed chlorine aluminium acidic ionic liquids dead catalyst,
The lower part of the shell is equipped with the filler support bracket for supporting filler, exhaust outlet is equipped at the top of the shell, described
The side wall of shell is equipped with oil discharge outlet, water inlet and feed inlet, and the oil discharge outlet is connected to the annular collection tank, the water inlet
It is connected to the water distributor, the feed inlet is connected to the distributing device, is equipped with liquid outlet in the bottom of the shell.
It is extremely strong in view of the acidity of dead catalyst, and viscosity is up to 600-800mPas, and has containing a small amount of machinery
Impurity, to prevent blocking and corrosion, it is preferred to use the Machinery Diaphragm Pump of fluoroplastics material conveys it;In addition, strong brine
In sodium chloride content be up to 15-22wt%, corrosivity is strong, it is preferred to use the centrifugal pump of stainless steel material conveys it.
In above-mentioned hydrolysis reactor, dead catalyst is mixed with strong brine carries out hydrolysis, and the acid in dead catalyst is molten
Property hydrocarbon separated with active component, the molten oil of acid of formation floats up to liquid level, after the collection of annular collection tank, then through oil discharge outlet and its pipe
Road is from sump oil storage tank is flowed into case freshening.In particular, water inlet and water distributor are separately positioned in above-mentioned hydrolysis reactor
The top of feed inlet and distributing device not only contributes to dispersion of the strong brine to dead catalyst, and can make dead catalyst
The region of hydrolysis avoids influence of the hydrolysis localized heat release to acid molten oil quality and the rate of recovery far from the molten oil reservoir of acid.
In addition, the active component contained in dead catalyst and acid-soluble hydrocarbon can generate the organic dirt of volatility in hydrolytic process
Object (VOCs) and hydrogen chloride are contaminated, is enriched at the top of hydrolysis reactor, in order to avoid being polluted to air, can hydrolyze
Exhaust outlet is arranged in the top of reactor, and gas is led to the water seal mouth of strong brine storage tank, and the strong brine in strong brine storage tank was both
These gaseous pollutants can be absorbed, while also can use liquid level and carrying out water seal;Water seal can also provide just for hydrolysis reactor
Pressure, promotes acidic hydrolysis liquid to the re-absorption of these pollutants.
In the present invention, the structure of the water distributor of hydrolysis reactor is not limited strictly, as long as it can make strong brine
It is uniformly distributed in hydrolysis reactor.
In concrete scheme of the invention, the water distributor includes cloth supply mains, is distinguished in the two sides of the cloth supply mains
Equipped with multiple parallel and spaced set water distribution branch pipes, multiple water distributing pores, water distribution is distributed in the bottom of each water distribution branch pipe
The total open area in hole accounts for 1% or more of the hydrolysis reactor sectional area.At this point, water distributor is fishbone type;Wherein, adjacent cloth
Spacing between water branch pipe can be set to 5cm or more, to avoid the floating for influencing the molten oil of acid and collect;In addition, to water distribution
The set-up mode of water distributing pore on branch pipe does not limit strictly, and multiple water distributing pores can be with spaced set, and can will be multiple
The aperture of water distributing pore is set as identical.
Water distributor perforated area with above structure is big, the number of openings is more, consequently facilitating promoting uniformly dividing for strong brine
Cloth;Further, since the flow velocity that portals of water distributing pore is small, back-mixing is low, Laminar Flow is formed in hydrolysis reactor, is reduced and is urged with useless
Mass transfer between agent, and it is smaller to the molten oil reservoir disturbance of acid on hydrolysis liquid level, it is more advantageous to the recycling of the molten oil of acid.
In the present invention, the structure of the distributing device of hydrolysis reactor is not limited strictly, as long as it can make useless catalysis
Agent is uniformly distributed in hydrolysis reactor.
In concrete scheme of the invention, the distributing device includes cloth general pipeline, is distinguished in the two sides of the cloth general pipeline
Equipped with multiple concentric and spaced set semicircle cloth branch pipes, it is distributed in the bottom of each semicircle cloth branch pipe multiple
Cloth hole, the total open area in cloth hole account for 2% or more of the hydrolysis reactor sectional area.At this point, distributing device is ring-like;Its
In, the spacing between adjacent cloth branch pipe can be set to 5cm or more, to avoid the floating for influencing the molten oil of acid and collect;This
Outside, the set-up mode in the cloth hole on cloth branch pipe is not limited strictly, multiple cloth holes can be with spaced set, and can
To set identical for the aperture in multiple cloth holes, the internal diameter in cloth hole for example can be set to 3-5mm.
Distributing device perforated area with above structure is big, cloth hole number is more, consequently facilitating dead catalyst cloth is uniform;
Further, since the internal diameter of cloth material mouth is small, dead catalyst is extruded with droplet, is more advantageous to its dispersion in strong brine.
In the present invention, neutralization reactor be used for the acidic hydrolysis liquid that generates the hydrolysis with comprising alkaline waste water
Lye mixing carry out neutralization reaction;The specific structure of neutralization reactor is not limited strictly, it can be conventional using this field
Neutralization reactor.
In concrete scheme of the invention, the neutralization reactor is complete mixing flow reactor;The neutralization reactor includes
Shell is successively arranged the water distributor for being distributed lye and the cloth for being distributed neutralizer on the top of the shell from top to bottom
Glassware, is equipped with side-feeding mixer at the middle part of the shell, exhaust outlet is equipped at the top of the shell, in the shell
Side wall is equipped with alkali inlet and inlet, and the alkali inlet is connected to the water distributor, and the inlet is connected to the distributing device,
Liquid outlet is equipped in the bottom of the shell.
The present inventor's studies have shown that be separately positioned on inlet and cloth for the alkali inlet of neutralization reactor and water distributor
The position of the top of device, the metal hydroxides wadding body that neutralization reaction can be made to generate is lower, to be not easy to plug water distributor.It is special
It is not using side-feeding mixer, to accelerate the mass transfer between acidic hydrolysis liquid and lye and neutralization reaction, while can also prevent
Wadding body premature precipitation is to block liquid outlet and its pipeline.
Preferably, acidic hydrolysis liquid of the centrifugal pump of fluoroplastics material to height containing chlorine can be used to convey;Alkali cleaning is useless
Water and external source lye height contain chlorine, are high containing alkali, and need accurately to be matched with acidic hydrolysis liquid to reach neutralization, therefore preferably use
The metering pump of fluoroplastics material conveys alkali-wash waste water and external source lye.Further, since acidic hydrolysis liquid and alkali-wash waste water
In carry a small amount of oil, N-process will cause enrichment of the VOCs at the top of neutralization reactor;It, can be with to prevent air pollution
Exhaust outlet is set at the top of neutralization reactor, and gas is led to the water seal mouth of strong brine storage tank, it is dense in strong brine storage tank
These gaseous pollutants had both can be absorbed in salt water, also can use liquid level and carried out water seal;Water seal can also provide for neutralization reactor
Positive pressure, to promote neutralizer to the re-absorption of these pollutants.
The structure of water distributor and distributing device to neutralization reactor does not limit strictly, as long as can make lye and acidity
Hydrolyzate is uniformly distributed in neutralization reactor, can use and structure identical in hydrolysis reactor;At this point, in water distributor
The total open area of water distributing pore accounts for 1% or more of neutralization reactor sectional area, during the total open area in cloth hole accounts in distributing device
With 2% or more of reactor cross section product.Alkali-wash waste water merge with external source lye after through by above-mentioned fishbone type water distributor in and
Water distribution in reactor, since the perforated area of water distributor is big, the number of openings is more, promote alkali-wash waste water and external source lye in and
Being uniformly distributed in reactor;In addition, acidic hydrolysis liquid matches liquid, the cloth via above-mentioned ring-like distributing device in neutralization reactor
The perforated area of glassware is small, the quantity of cloth material mouth is few, internal diameter is small, forms local turbulence after liquid out, facilitate acidic hydrolysis liquid with
Mass transfer and neutralization reaction between lye.
In the present invention, flocculation sedimentation system is for the neutralizer that the neutralization reaction generates to be sufficiently mixed with flocculant
And implement sedimentation separation;The specific structure of flocculation sedimentation system is not limited strictly, the structure of this field routine can be used.
In concrete scheme of the invention, the flocculation sedimentation system includes that the pipe-line mixer set gradually and flocculation are heavy
Shallow lake device, the flocculation deposition apparatus include seal casinghousing, be equipped with inside the seal casinghousing annular overflow weir, central tube and
The inside of the central tube is arranged in cloth tube, the cloth tube, umbellate form baffle is equipped in the bottom of the central tube, described
The top of seal casinghousing be equipped with exhaust outlet, the seal casinghousing side wall be equipped with water outlet and feed inlet, the water outlet with
The annular overflow weir connection, the feed inlet are connected to the cloth tube, are equipped with slag notch in the bottom of the seal casinghousing.
It is understood that the liquid outlet of neutralization reactor is connect with the import of pipe-line mixer by the road, it is in and anti-
It answers device liquid outlet and the connecting line of pipe-line mixer import is equipped with plus agent mouth, flocculating agent formulation tank goes out agent mouth through stainless steel
The metering pump and pipeline of material are connect with agent mouth is added.In the present invention, pipe-line mixer be easy to implement neutralizer and flocculant it
Between come into full contact with;In addition, carrying out adding agent using the metering pump of stainless steel material, convenient for matching flocculant accurately with neutralizer
With the flocculating effect being optimal.
In the present invention, the flocculation deposition apparatus with above structure is the vertical sedimentation basin form of sealing;Contain wadding
The neutralizer and flocculant of body are sufficiently mixed through pipe-line mixer, carry out precipitating point into above-mentioned flocculation deposition apparatus through gravity flow
From the moisture content that wadding body is concentrated reduces, and alleviates the processing load of subsequent mechanical dehydration device, while the strong brine of Precipitation
Hydrolysis reactor can be back to.Since the material in flocculation deposition apparatus is possible to evolution gaseous pollutant, using sealing
Form, while exhaust outlet is set at the top of it, gas is led into the progress water seal of strong brine storage tank.In particular, based on separation equipment
Maturity and operational simplicity carry out strong brine and wadding body using the flocculation deposition apparatus of above-mentioned vertical sedimentation basin form
Separation;Neutralizer through feed inlet enters flocculation deposition apparatus after mixing with flocculant, during cloth tube squeezes into downwards neutralizer
Heart pipe, through umbellate form baffle baffling, metal hydroxides wadding body is concentrated to the bottom precipitation of flocculation deposition apparatus;Meanwhile strong brine
Enter strong brine storage tank to the top lift of flocculation deposition apparatus, and through annular overflow weir and water outlet gravity flow.It is certain when reaching
Sedimentation time, the interface being concentrated between wadding body and strong brine is clear, and strong brine is carried secretly almost without wadding body.
Being carried out dehydrating using mechanical dehydration device to concentration wadding body can be significantly reduced solid slag amount.In view of concentration wadding body
Solid content be about 2-3wt%, and contain strong brine, therefore the screw pump of stainless steel material can be selected to be conveyed.This
Outside, the moisture in wadding body is concentrated based on Free water, therefore can get using conventional plate and frame filter press or centrifugal dehydrator
Good dehydrating effect.Have the shortcomings that land occupation is big, the processing time is long in view of plate and frame filter press, cannot operate continuously, therefore machine
Tool dehydration device is preferably centrifugal dehydrator, and separation factor can be 3000 or so, at this time can be prepared into concentration wadding body
Moisture content is the wet solid slag of 60-70%.
It can continue to reduce solid slag yield since wet solid slag is dried, and be more advantageous to reuse, therefore this hair
Desiccation apparatus is arranged so that the wet solid slag formed through the mechanical dehydration device is dried in bright system.In the present invention
In, wet solid slag can be conveyed using screw conveyor;The mode of movement is cleaner, avoids the scaling-off of belt transmission
Phenomena such as.
Further, the desiccation apparatus can use thin layer desiccation machine or low temperature dehumidification desiccation machine, can be by wet solid slag
Dry is the solid slag of moisture content 10-20%.Since the moisture in solid slag is mainly the crystallization water, continue to reduce moisture content not only
Low efficiency and uneconomical.
In addition, the moisture in wet solid slag can be converted into water vapour during removal moisture drying, recycles vapour latent heat and return
It uses drying process and is more advantageous to reduction energy consumption.Therefore, system of the invention can also include heat reclaim unit (i.e. condensed water
Storage tank), it is used to recycle the condensed water that above-mentioned desiccation apparatus generates;Since the pollutional load for recycling obtained condensed water is low, because
This can be back to the preparation of external source lye and flocculant.
It is understood that system of the invention is other than including aforementioned body component, it can also include other mating
Component, for example, it is dead catalyst storage tank, strong brine storage tank, alkali-wash waste water storage tank, external source Alkali liquid compounding tank, flocculating agent formulation tank, solidifying
Storage tank, sump oil storage tank and various for conveying pump and conveyer of material etc. are born water, the routine of this field can be used
Device or component, and can be configured in a usual manner.
In the present invention, dead catalyst storage tank includes tank body, side-feeding mixer is equipped in tank interior, in tank wall
Lower end is equipped with inlet port and outlet port, is equipped with evacuation port in tank base, is equipped with gas feed in top of the tank;Wherein, side into
Formula blender is used to carry out the dead catalyst from different periods homogeneous average, and gas feed is used for dead catalyst storage tank
Tank deck inflated with nitrogen is protected, and to avoid the contact with moisture in dead catalyst and air, prevents hydrolysis from exploding.
In the present invention, strong brine storage tank includes tank body and water sealing (sealing water) pipe, water inlet is equipped in tank wall upper end, in tank body
Side wall lower ends are equipped with water outlet, are equipped with evacuation port in tank base, are equipped with water seal mouth in top of the tank, water sealing (sealing water) pipe and water seal mouth connect
It connects.Strong brine storage tank is set and not only provided space for the storage of intermediate product strong brine, but also provides raw material for hydrolysis, is
The key node that whole system intermediate product recycles;Meanwhile hydrolysis reactor, neutralization reaction can also be controlled by water seal
The evolution of gaseous pollutant, avoids air pollution in device and flocculation deposition apparatus.
In the present invention, alkali-wash waste water storage tank includes tank body, side-feeding mixer is equipped in tank interior, in tank wall
Lower end is equipped with water inlet and water outlet, is equipped with evacuation port in tank base;Wherein, when side-feeding mixer is used for coming from different
The alkali-wash waste water of section carries out homogeneous average.
In the present invention, condensation water storage tank includes tank body, water inlet is equipped in tank wall upper end, in tank wall lower end
Equipped with condensation water out, evacuation port is equipped in tank base.The storage that condensation water storage tank had both been intermediate product condensed water is arranged to mention
For space, and the preparation for external source lye and flocculant provides water source, and it is important to be that whole system intermediate product recycles
Node.
Further, system of the invention includes Machinery Diaphragm Pump and centrifugal pump, and the dead catalyst storage tank passes through described
Machinery Diaphragm Pump is connect with the feed inlet of the hydrolysis reactor, and the strong brine storage tank passes through the centrifugal pump and the hydrolysis
The water inlet of reactor connects, and the oil discharge outlet of the hydrolysis reactor is connect with sump oil storage tank.
Further, system of the invention includes centrifugal pump and metering pump, and the liquid outlet of the hydrolysis reactor passes through institute
It states centrifugal pump to connect with the inlet of the neutralization reactor, the alkali-wash waste water storage tank and external source Alkali liquid compounding tank pass through respectively
The metering pump is connect with the alkali inlet of the neutralization reactor, the liquid outlet of the neutralization reactor and the pipe-line mixer
Connection.
Further, system of the invention includes metering pump, and the condensation water storage tank passes through the metering pump and outer respectively
The water inlet connection of the water inlet and flocculating agent formulation tank of source Alkali liquid compounding tank.Condensed water is conveyed using metering pump, convenient for external
The concentration of source lye and flocculant is accurately controlled.
In particular, the exhaust outlet of the exhaust outlet of the hydrolysis reactor, the neutralization reactor, the flocculation sedimentation system
Water outlet and exhaust outlet pass through pipeline respectively and connect with the water seal mouth of strong brine storage tank.
In addition, the flocculation sedimentation system and mechanical dehydration device have brine outlet, the brine outlet and institute
The connection of strong brine storage tank is stated, consequently facilitating carrying out reuse to strong brine.
System of the invention be for chlorine aluminium acidic ionic liquids dead catalyst and with the characteristic of alkali-wash waste water and propose,
Its innoxious and oils resource reclaim that dead catalyst and alkali-wash waste water are realized using hydrolysis reactor and neutralization reactor, and
And the minimizing and recycling of metal solid slag are realized using flocculation sedimentation system, mechanical dehydration device and desiccation apparatus;In addition,
Recycling for intermediate product is realized using strong brine storage tank and condensation water storage tank.The operational process of whole system is mild, behaviour
Make process safety, no new pollution source is high to the rate of recovery of resource, especially recycles containing for the obtained molten W/O of acid and impurity
Measure low, the quality height of oil product.
Detailed description of the invention
Fig. 1 is being handled chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water for an embodiment of the present invention
Process flow chart;
Fig. 2 is the processing chlorine aluminium acidic ionic liquids dead catalyst of an embodiment of the present invention and the system of alkaline waste water
Structural schematic diagram;
Fig. 3 is the structural schematic diagram of the hydrolysis reactor of an embodiment of the present invention;
Fig. 4 is the Section A-A schematic diagram of Fig. 3;
Fig. 5 is the structural schematic diagram of the annular collection tank of the hydrolysis reactor of an embodiment of the present invention;
Fig. 6 is the structural schematic diagram of the water distributor of an embodiment of the present invention;
Fig. 7 is the structural schematic diagram of the distributing device of an embodiment of the present invention;
Fig. 8 is the section B-B schematic diagram of Fig. 7;
Fig. 9 is the structural schematic diagram of the neutralization reactor of an embodiment of the present invention;
Figure 10 is the structural schematic diagram of the flocculation deposition apparatus of an embodiment of the present invention.
Description of symbols:
1: hydrolysis reactor;11: shell;12: annular collection tank;13: water distributor;14: distributing device;15: filler support bracket;
16: exhaust outlet;17: oil discharge outlet;18: water inlet;19: feed inlet;110: liquid outlet;111: overflow weir;112: packing layer;
2: neutralization reactor;21: shell;22: water distributor;23: distributing device;24: side-feeding mixer;25: exhaust outlet;
26: alkali inlet;27: inlet;28: liquid outlet;
3: flocculation deposition apparatus;31: seal casinghousing;32: annular overflow weir;33: central tube;34: cloth tube;35: umbellate form
Baffle;36: exhaust outlet;37: water outlet;38: feed inlet;39: slag notch;
4: mechanical dehydration device;5: desiccation apparatus;
61: dead catalyst storage tank;611: gas feed;62: strong brine storage tank;63: alkali-wash waste water storage tank;64: external source alkali
Liquid preparing tank;65: flocculating agent formulation tank;66: condensation water storage tank;67: sump oil storage tank;
71: Machinery Diaphragm Pump;72,77: centrifugal pump;73,74,75,76: metering pump;78: screw pump;
8: pipe-line mixer;9: screw conveyor;10: feed bin;
101: cloth supply mains;102: water distribution branch pipe;
201: cloth general pipeline;202: cloth branch pipe;203: cloth hole.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The raw material of each embodiment is as follows:
Chlorine aluminium acidic ionic liquids dead catalyst: it is produced to produce alkylate oil using the ionic liquid-catalyzed carbon four of chlorine aluminic acid class
Raw dead catalyst, viscosity are about 740mPas, and active component is mainly aluminium chloride and copper chloride, and total content accounts for about 85wt%;
Other components are acid-soluble hydrocarbon, and content accounts for about 15wt%.
Alkaline waste water: to produce the alkali-wash waste water that alkylate oil generates, hydrogen using the ionic liquid-catalyzed carbon four of chlorine aluminic acid class
Aoxidizing na concn is about 12wt%.
To the method that above-mentioned chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water are handled, specifically include: firstly,
Chlorine aluminium acidic ionic liquids dead catalyst is mixed with strong brine and carries out hydrolysis, until completely eliminating the residual of dead catalyst
Activity generates acidic hydrolysis liquid and the molten oil of acid, and the molten oil of acid is separated with acidic hydrolysis liquid to upper layer through sedimentation to be recovered;Then, will
Acidic hydrolysis liquid, alkali-wash waste water and the mixing of the external source of preparation lye carry out neutralization reaction, until system is alkalescent, generation contains
There is the neutralizer of metal hydroxides wadding body;Sedimentation separation is carried out after neutralizer and flocculant are sufficiently mixed, bottom generates dense
Contracting wadding body, the strong brine that upper layer is precipitated are back to the hydrolysis with dead catalyst;Mechanical dehydration is carried out to above-mentioned concentration wadding body
Processing generates the wet solid slag of moisture content about 60-70wt%, and the strong brine isolated from concentration wadding body is back to dead catalyst
Hydrolysis;Above-mentioned wet solid slag is dried, the desiccation solid slag of moisture content about 10-20wt% is generated, drying process produces
Raw water vapour is back to the preparation of external source lye and flocculant solution after condensing.
Embodiment 1
By taking yield is 300,000 tons/year of chlorine aluminic acid class compound ion liquid alkyl plant as an example, which was being produced
The amount that journey discharges dead catalyst is 2140 tons/year, and it is stand-by that dead catalyst comes together in the storage of dead catalyst storage tank;Meanwhile the device
It is 6340 tons/year in the amount of production process discharge alkali-wash waste water.
As shown in Figure 1, the method for the present embodiment processing chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, step is such as
Under:
1, reagent preparation
Compound concentration is the sodium chloride solution (i.e. strong brine) of 15wt% or so in strong brine storage tank, is stored for future use.
Compound concentration is the sodium hydroxide solution (i.e. external source lye) of 30wt% or so in Alkali liquid compounding tank, is stored standby
With.
Compound concentration is the flocculant solution of 0.5wt% or so in flocculating agent formulation tank, is stored for future use;Wherein, it flocculates
Agent is anionic polyacrylamide, and relative molecular weight is 15,000,000, charge density 20%.
Mentioned reagent is all made of fresh water (such as tap water) before going into operation and is prepared;After operation, lye and flocculation
The preparation of agent uses the condensed water from desiccation apparatus, and the preparation of strong brine is used to be filled from flocculation deposition apparatus and mechanical dehydration
The strong brine set.
2, hydrolysis
The dead catalyst of 255kg/h is promoted through fluoroplastics Machinery Diaphragm Pump, and the strong brine of 12457kg/h is centrifuged through stainless steel
Pump is promoted, and dead catalyst and strong brine respectively enter hydrolysis reactor and reaction are hydrolyzed with by the input material volume ratio of 1:50.Water
Solution reaction carries out in plug flow packed bed reactor, and structured packing is filled in plug flow packed bed reactor, catalysis of giving up
Agent is hydrolyzed with the fluidised form of plug flow in packing layer with strong brine reacts;Wherein, the Y of polyvinyl chloride material is selected in structured packing
Type ripple orifice plate structured packing, specific surface area 350m2/m3, porosity 0.95m3/m3, the sky of hydrolysis reactor packing layer
Speed control is in 0.25h-1.2.6 or so, the residual activity of dead catalyst is disappeared pH stable to hydrolysis product completely
It removes.
Sedimentation separation is carried out to hydrolysis product, respectively obtains acidic hydrolysis liquid and the molten oil of acid;Wherein, acidic hydrolysis liquid
PH value be 2.6 or so, oil content is about 120mg/L;Meanwhile the molten oil of acid of 40kg/h or so enters sump oil by gravity flow recycling
It is stored in storage tank.The composition of the molten oil of acid is cyclopentadiene compound, can periodically be sent to delayed coking unit conduct
Raw material recycles.
3, neutralization reaction
The acidic hydrolysis liquid of 12672kg/h is promoted through fluoroplastics centrifugal pump, 754kg/h alkali-wash waste water and 251kg/h external source
Lye is promoted through fluoroplastics metering pump, and acidic hydrolysis liquid, alkali-wash waste water and external source lye are distinguished by the input material volume ratio of 50:3:1
Into carrying out neutralization reaction in neutralization reactor.Neutralization reaction carries out in complete mixing flow reactor, acidic hydrolysis liquid, alkali-wash waste water
Quick neutralization reaction is carried out with the fluidised form of complete mixing flow with external source lye;Wherein, the air speed of neutralization reactor is controlled in 1h-1, in
When reaching 8.5 or so with the pH value of liquid, acidic hydrolysis liquid complete neutralization, the oil content of neutralizer is about 120mg/L, chlorination at this time
Sodium content is about 20wt%, and aluminium hydroxide/Kocide SD wadding body content is about 2.8wt%.
4, it flocculates
The flocculant solution of 0.5wt% is added into neutralizer, the mass ratio for controlling neutralizer and flocculant solution is
230:1 (i.e. flocculant dosage is that flocculant 22g or so is added in neutralizer per ton), after being sufficiently mixed in pipe-line mixer,
Gravity flow, which enters in flocculation deposition apparatus, carries out sedimentation separation.
After implementing sedimentation separation 2 hours, concentration wadding body layer volume accounts for 25% left side of volume of material in flocculation deposition apparatus
The right side, the strong brine content that wadding body is concentrated is about 90wt%.The 75wt% of volume of material is strong brine, petroleum in flocculation deposition apparatus
Class content is about 150mg/L, and strong brine is back to hydrolysis reactor from strong brine storage tank is flowed into.
5, dehydration
Concentration wadding body delivers into centrifugal dehydrator (i.e. mechanical dehydration device) through stainless steel screw pump and is carried out dehydrating,
Wherein the separation factor of centrifugal dehydrator is 3000 or so;The wet solid slag self-unloading that the moisture content that dehydration generates is 70wt% or so into
Enter feed bin, the strong brine oil content isolated from concentration wadding body is 100mg/L, and strong brine flows into strong brine storage tank, reuse certainly
In hydrolysis reactor.
6, it is dried
Wet solid slag in feed bin is sent into thin layer desiccation machine (i.e. desiccation apparatus) through stainless steel spiral conveyer, generates 454kg/
The moisture content of h is the solid slag of 15wt%.The content of sodium chloride is about 54.7wt% in the solid slag, and the content of aluminium hydroxide is about
For 22.5wt%, the content of Kocide SD is about 6.7wt%, and oil content is less than 1wt%, can be used as general solid waste factory or
It is utilized as metallurgical raw material.
The condensed water CODcr that thin layer desiccation machine drying process generates is about 500mg/L, hardly oil-containing and salt, gravity flow
Into condensation water storage tank, it is back to the preparation of lye and flocculant solution.
After above-mentioned processing, the rate of recovery of the molten oil of acid reaches 90% or so in dead catalyst;In addition, being recycled through detecting
The moisture content of the molten oil of acid arrived is 1wt% or so, and carbon particle impurity is not detected, and the quality for recycling oil product is high.
Embodiment 2
The method that the present embodiment handles chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, steps are as follows:
1, reagent preparation
Compound concentration is the sodium chloride solution (i.e. strong brine) of 22wt% or so in strong brine storage tank, is stored for future use.
Compound concentration is the sodium hydroxide solution (i.e. external source lye) of 30wt% or so in Alkali liquid compounding tank, is stored standby
With.
Compound concentration is the flocculant solution of 0.5wt% or so in flocculating agent formulation tank, is stored for future use;Wherein, it flocculates
Agent is anionic polyacrylamide, and relative molecular weight is 18,000,000, charge density 10%.
Mentioned reagent is all made of fresh water (such as tap water) before going into operation and is prepared;After operation, lye and flocculation
The preparation of agent uses the condensed water from desiccation apparatus, and the preparation of strong brine is used to be filled from flocculation deposition apparatus and mechanical dehydration
The strong brine set.
2, hydrolysis
Dead catalyst is promoted through fluoroplastics Machinery Diaphragm Pump, and strong brine is promoted through stainless steel centrifugal pump, dead catalyst with it is dense
Salt water and the input material volume ratio for pressing 1:60, respectively enter hydrolysis reactor and reaction are hydrolyzed.Hydrolysis is filled in plug flow
It is carried out in bed reactor, structured packing is filled in plug flow packed bed reactor, dead catalyst and strong brine are with plug flow
Fluidised form reaction is hydrolyzed in packing layer;Wherein, structured packing selects the Y type ripple orifice plate of polyvinyl chloride material is regular to fill out
Material, specific surface area 500m2/m3, porosity 0.97m3/m3, the air speed control of hydrolysis reactor packing layer is in 0.5h-1.To
2.6 or so, the residual activity of dead catalyst is completely eliminated the pH stable of hydrolysis product.
Sedimentation separation is carried out to hydrolysis product, respectively obtains acidic hydrolysis liquid and the molten oil of acid;Wherein, acidic hydrolysis liquid
PH value be 2.6 or so, oil content is about 120mg/L;Meanwhile the molten oil of acid is recycled to enter in sump oil storage tank by gravity flow and be stored up
It deposits.The composition of the molten oil of acid is cyclopentadiene compound, can periodically be sent to delayed coking unit and recycle as raw material.
3, neutralization reaction
Acidic hydrolysis liquid is promoted through fluoroplastics centrifugal pump, and alkali-wash waste water and external source lye are promoted through fluoroplastics metering pump, acid
Property hydrolyzate, alkali-wash waste water and external source lye respectively enterd by certain input material volume ratio carry out neutralizing in neutralization reactor it is anti-
It answers, makes concentration 30wt% of sodium chloride in neutralizer or so.Neutralization reaction carries out in complete mixing flow reactor, acidic hydrolysis
Liquid, alkali-wash waste water and external source lye carry out quick neutralization reaction with the fluidised form of complete mixing flow;Wherein, the air speed control of neutralization reactor
System is in 2h-1, when the pH value of neutralizer reaches 8.5 or so, acidic hydrolysis liquid complete neutralization, at this time the oil content of neutralizer be about
60mg/L, sodium chloride content are about 23wt%, and aluminium hydroxide/Kocide SD wadding body content is about 2.8wt%.
4, it flocculates
The flocculant solution of 0.5wt% is added into neutralizer, control flocculant dosage is that wadding is added in neutralizer per ton
Solidifying agent 30g or so, after being sufficiently mixed in pipe-line mixer, gravity flow, which enters in flocculation deposition apparatus, carries out sedimentation separation.
After implementing sedimentation separation 3 hours or so, concentration wadding body layer volume accounts for volume of material in flocculation deposition apparatus
20% or so, the strong brine content that wadding body is concentrated is about 85wt%.The 97wt% of volume of material is dense salt in flocculation deposition apparatus
Water, petroleum content are about 50mg/L, and strong brine is back to hydrolysis reactor from strong brine storage tank is flowed into.
5, dehydration
Concentration wadding body delivers into centrifugal dehydrator (i.e. mechanical dehydration device) through stainless steel screw pump and is carried out dehydrating,
Wherein the separation factor of centrifugal dehydrator is 3000 or so;The wet solid slag self-unloading that the moisture content that dehydration generates is 70wt% or so into
Enter feed bin, the strong brine oil content isolated from concentration wadding body is 50mg/L, and strong brine is back to from strong brine storage tank is flowed into
Hydrolysis reactor.
6, it is dried
Wet solid slag in feed bin is sent into thin layer desiccation machine (i.e. desiccation apparatus) through stainless steel spiral conveyer, generates moisture content
For the solid slag of 15wt% or so.The content of sodium chloride is about 55wt% in the solid slag, and the content of aluminium hydroxide is about
22wt%, the content of Kocide SD are about 7wt%, and oil content is less than 1wt%, can be used as general solid waste factory or as smelting
Golden raw material utilizes.
The condensed water CODcr that thin layer desiccation machine drying process generates is about 500mg/L, hardly oil-containing and salt, gravity flow
Into condensation water storage tank, it is back to the preparation of lye and flocculant solution.
After above-mentioned processing, the rate of recovery of the molten oil of acid reaches 90% or so in dead catalyst;In addition, being recycled through detecting
The moisture content of the molten oil of acid arrived is 1wt% or so, and carbon particle impurity is not detected, and the quality for recycling oil product is high.
Embodiment 3
In conjunction with shown in Fig. 2 to Figure 10, processing chlorine aluminium acidic ionic liquids dead catalyst of the invention and alkaline waste water are
System, including hydrolysis reactor 1, neutralization reactor 2, flocculation sedimentation system, mechanical dehydration device 4 and desiccation apparatus 5;Hydrolysis
Device 1, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis;Neutralization reactor 2 and hydrolysis are anti-
Device 1 is answered to connect, the acidic hydrolysis liquid for generating hydrolysis is mixed with the lye comprising alkaline waste water carries out neutralization reaction;
Flocculation sedimentation system is connect with neutralization reactor 2, and the neutralizer for generating neutralization reaction and flocculant are sufficiently mixed simultaneously in fact
Apply sedimentation separation;Mechanical dehydration device 4 is connect with flocculation sedimentation system, for carrying out to the concentration wadding body formed through sedimentation separation
Dehydration;Desiccation apparatus 5 is connect with mechanical dehydration device 4, for place to be dried to the wet solid slag formed through dehydration
Reason.
System of the invention is by being respectively set hydrolysis reactor 1 and neutralization reactor 2, thus being urged using lye useless
Before agent carries out neutralization reaction, first chlorine aluminium acidic ionic liquids dead catalyst is mixed in hydrolysis reactor 1 with strong brine
Reaction is hydrolyzed;In hydrolysis reactor 1, a large amount of strong brine can be by hydrolysis in the hydrolytic process of dead catalyst
The hot rapid dispersion generated, so that the autoacceleration mechanism of hydrolysis be interrupted;Meanwhile the chloride ion of strong brine middle and high concentration increases
The concentration for having added hydrolysate has certain inhibiting effect to hydrolysis.Aforesaid way can not only leniently be eliminated useless
The activity of catalyst, while neutralization reaction heat can be eliminated to the facilitation of hydrolysis reaction, make the operation of whole system
Process is more stable and safe.
The method that system of the invention can be used for embodiment 1 or embodiment 2;Below to the knot of each component of present system
Structure is described in detail.
1, hydrolysis reactor
In one embodiment, hydrolysis reactor 1 is set as plug flow packed bed reactor, can make hydrolysis more
Heating and, to realize mild hydrolysis;At this point, dead catalyst and strong brine are in hydrolysis reactor 1 with the progress of flat-pushing stream mode
Contact, the back-mixing degree of material is low, and small to the disturbance of dead catalyst drop, the mass transfer between active component and moisture is weakened,
The intensity of hydrolysis is not only reduced, and is conducive to the separation and recycling of the molten oil of acid.
Further, structured packing is filled in plug flow packed bed reactor, which fully utilizes dead catalyst
High viscosity characteristic, filler surface behavior of boundary layer and filler to the crown_interception of catalyst;Due to dead catalyst
Viscosity is high, inlet amount is small, is in membranaceous Laminar Flow on structured packing surface, and form thicker laminar boundary layer, larger
Stickiness power so that the rate of settling of dead catalyst is effectively controlled.Further, since the presence of inner layer of boundary layer laminar sublayer, storeroom
Resistance to mass tranfer increase, therefore the mass-transfer efficiency between dead catalyst and strong brine is also effectively controlled.Relative to random packing,
The material flow passage of structured packing is uniform, is less prone to channeling.
In particular, unobstructed flow path, and basic retaining layer can be provided by using high-throughput structured packing for strong brine
Stream mode, while the mass transfer between dead catalyst can be weakened.When reaction is hydrolyzed, dead catalyst is in the hole of structured packing
It being uniformly distributed in gap, the numerous elementary reaction environment of forming quantity, the strong brine of the big scale of construction and the time of contact of dead catalyst are long,
To ensure that the thorough hydrolysis to dead catalyst.Specifically, the porosity of structured packing is 0.95-0.97m3/m3, specific surface
Product is in 300-500m2/m3;At this point, the rate control of hydrolysis is preferable, neither duct is easily caused to block, while hydrolysis is easy
It carries out completely.
Further, structured packing can be oleophobic property filler and can have inclined plate structure;The structured packing can also
Enough coarses promoted to the molten oil droplet of acid make bulky grain oil droplet be easier to float, to be conducive to the recycling of the molten oil of acid.The present invention
Specific structure and material to structured packing do not limit strictly;Structured packing for example can be the orifice plate structured packing of Y type ripple
Deng the inclination angle of ripple and axis can be 45 ° or so, so that the rejection effect to dead catalyst drop is good.In addition, regular fill out
The material of material can be polyethylene (PE), polyvinyl chloride (PVC) or Kynoar (PVDF), with oleophobic property and acidproof resistance to
Chlorine corrosion is conducive to the coarse of the molten oil of acid, consequently facilitating the molten oil recycling of acid.
In particular, the air speed of above-mentioned plug flow packed bed reactor can be 0.25-0.5h-1.Wherein, when air speed is
0.5h-1When, dead catalyst is able to complete hydrolysis, and pH value can be stablized in 2.5-2.8;When air speed is 0.25h-1When, acidic hydrolysis
The oil content of liquid is minimum, and the molten oil of the acid recycled is at most.
In conjunction with shown in Fig. 3 to Fig. 5, hydrolysis reactor 1 includes shell 11, is successively arranged from top to bottom on the top of shell 11
Annular collection tank 12, the water distributor 13 for being distributed strong brine and the cloth for being distributed chlorine aluminium acidic ionic liquids dead catalyst
Device 14, is equipped with the filler support bracket 15 for supporting filler in the lower part of shell 11, is equipped with exhaust outlet 16 at the top of shell 11,
It is equipped with oil discharge outlet 17, water inlet 18 and feed inlet 19 in the side wall of shell 11, oil discharge outlet 17 is connected to annular collection tank 12, intakes
Mouth 18 is connected to water distributor 13, and feed inlet 19 is connected to distributing device 14, is equipped with liquid outlet 110 in the bottom of shell 11.
It is understood that above-mentioned structured packing is seated on filler support bracket 15 (referring to fig. 4), to form packing layer
112;Further, it is also possible to overflow weir 111 be arranged in the top of annular collection tank 12, to maintain oil reservoir and the molten oil of acid to be made uniformly to overflow
Out.
Further, extremely strong in view of the acidity of dead catalyst, and viscosity is up to 600-800mPas, and have containing
A small amount of mechanical admixture, to prevent blocking and corrosion, it is preferred to use the Machinery Diaphragm Pump 71 of fluoroplastics material conveys it;
In addition, the sodium chloride content in strong brine is up to 15-22wt%, corrosivity is strong, it is preferred to use the centrifugal pump 72 of stainless steel material
It is conveyed.
In above-mentioned hydrolysis reactor 1, dead catalyst is mixed with strong brine carries out hydrolysis, and the acid in dead catalyst is molten
Property hydrocarbon separated with active component, the molten oil of acid of formation floats up to liquid level, after the collection of annular collection tank 12, then through oil discharge outlet 17 and
Its pipeline is from sump oil storage tank 67 is flowed into case freshening (referring to Fig. 5).In particular, in above-mentioned hydrolysis reactor 1, by water inlet 18
And water distributor 13 is separately positioned on the top of feed inlet 19 and distributing device 14, not only contributes to strong brine and divides dead catalyst
It dissipates, and it is molten to acid to avoid hydrolysis localized heat release far from the molten oil reservoir of acid for the region that can make dead catalyst that hydrolysis occur
The influence of oil quality and the rate of recovery.
In addition, the active component contained in dead catalyst and acid-soluble hydrocarbon can generate the organic dirt of volatility in hydrolytic process
Object (VOCs) and hydrogen chloride are contaminated, is enriched at the top of hydrolysis reactor 1, it, can be in water in order to avoid being polluted to air
Exhaust outlet 16 is arranged in the top for solving reactor 1, and gas is led to the water seal mouth of strong brine storage tank 62, in strong brine storage tank 62
These gaseous pollutants had both can be absorbed in strong brine, while also can use liquid level and carrying out water seal;Water seal can also be hydrolysis
Device 1 provides positive pressure, promotes acidic hydrolysis liquid to the re-absorption of these pollutants.
In the present invention, the structure of the water distributor 13 of hydrolysis reactor 1 and distributing device 14 is not limited strictly, as long as its
Strong brine and dead catalyst can be made to be uniformly distributed in hydrolysis reactor 1.
Specifically, as shown in fig. 6, in one embodiment, water distributor 13 includes cloth supply mains 101, in cloth supply mains 101
Two sides be respectively equipped with multiple parallel and spaced set water distribution branch pipes 102, be distributed in the bottom of each water distribution branch pipe 102
Multiple water distributing pores (not shown), the total open area of water distributing pore account for 1% or more of 1 sectional area of hydrolysis reactor.At this point, water distributor
13 be fishbone type;Wherein, the spacing between adjacent water distribution branch pipe 102 can be set to 5cm or more, to avoid influencing the molten oil of acid
Floating and collect;In addition, the set-up mode to the water distributing pore on water distribution branch pipe 102 does not limit strictly, multiple water distributing pores can
With spaced set, and it can set identical for the aperture of multiple water distributing pores.
The perforated area of water distributor 13 with above structure is big, the number of openings is more, consequently facilitating promoting the equal of strong brine
Even distribution;Further, since the flow velocity that portals of water distributing pore is small, back-mixing is low, Laminar Flow is formed in hydrolysis reactor 1, is reduced
Mass transfer between dead catalyst, and it is smaller to the molten oil reservoir disturbance of acid on hydrolysis liquid level, it is more advantageous to the recycling of the molten oil of acid.
As shown in Figure 7 and Figure 8, in one embodiment, distributing device 14 includes cloth general pipeline 201, cloth general pipeline's 201
Two sides are respectively equipped with multiple concentric and spaced set semicircle cloth branch pipes 202, in each semicircle cloth branch pipe 202
Multiple cloth holes 203 (referring to Fig. 7) are distributed in bottom, and the total open area in cloth hole 203 accounts for 1 sectional area of hydrolysis reactor
2% or more.At this point, distributing device 14 is ring-like;Wherein, the spacing between adjacent cloth branch pipe 202 can be set to 5cm or more,
To avoid the floating for influencing the molten oil of acid and collect;In addition, not making to the set-up mode in the cloth hole 203 on cloth branch pipe 202
Stringent limitation, multiple cloth holes 203 can be with spaced set, and can set identical for the aperture in multiple cloth holes 203,
The internal diameter in cloth hole 203 for example can be set to 3-5mm.
The perforated area of distributing device 14 with above structure is big, cloth hole number is more, consequently facilitating dead catalyst cloth
Uniformly;Further, since the internal diameter in cloth hole 203 is small, dead catalyst is extruded with droplet, is more advantageous to it in strong brine
Dispersion.
2, neutralization reactor
Neutralization reactor 2 is used to the acidic hydrolysis liquid that hydrolysis generates mixing progress with the lye comprising alkaline waste water
Neutralization reaction;The specific structure of neutralization reactor 2 is not limited strictly, the neutralization reactor of this field routine can be used.
Specifically, neutralization reactor 2 is set as complete mixing flow reactor;As shown in figure 9, neutralization reactor 2 includes shell 21,
It is successively arranged the water distributor 22 for being distributed lye and the distributing device for being distributed neutralizer from top to bottom on the top of shell 21
23, it is equipped with side-feeding mixer 24 at the middle part of shell 21, exhaust outlet 25 is equipped at the top of shell 21, in the side wall of shell 21
Equipped with alkali inlet 26 and inlet 27, alkali inlet 26 is connected to water distributor 22, and inlet 27 is connected to distributing device 23, in shell 21
Bottom be equipped with liquid outlet 28.
The alkali inlet 26 of neutralization reactor 2 and water distributor 22 are arranged in the top of inlet 27 and distributing device 23, it can
The position for the metal hydroxides wadding body for generating neutralization reaction is lower, to be not easy to plug water distributor 22.In particular, using side
Feeding mixer 24 accelerates the mass transfer between acidic hydrolysis liquid and lye and neutralization reaction, while also wadding body can be prevented too early
Precipitating is to block liquid outlet 28 and its pipeline.
Preferably, it can be conveyed using acidic hydrolysis liquid of the 77 pairs of height of centrifugal pump containing chlorine of fluoroplastics material;Alkali cleaning
Waste water and external source lye height contain chlorine, are high containing alkali, and need accurately to be matched with acidic hydrolysis liquid to reach neutralization, therefore preferably adopt
It is conveyed with 73,74 pairs of alkali-wash waste waters of metering pump and external source lye of fluoroplastics material.Further, since acidic hydrolysis liquid and alkali
It washes and carries a small amount of oil in waste water, N-process will cause VOCs in the enrichment at 2 top of neutralization reactor;To prevent air dirty
Dye can be arranged exhaust outlet 25 at the top of neutralization reactor 2, and gas is led to the water seal mouth of strong brine storage tank 62, dense salt
These gaseous pollutants had both can be absorbed in strong brine in water storage tank 62, also can use liquid level and carried out water seal;Water seal can also be
Neutralization reactor 2 provides positive pressure, to promote neutralizer to the re-absorption of these pollutants.
The structure of water distributor 22 and distributing device 23 to neutralization reactor 2 does not limit strictly, as long as can make lye
It is uniformly distributed in neutralization reactor 2 with acidic hydrolysis liquid, can be used and identical structure in hydrolysis reactor 1.Alkali cleaning
Waste water passes through the water distribution in neutralization reactor 2 of water distributor 22 by above-mentioned fishbone type after merging with external source lye, due to water distributor 22
Perforated area is big, the number of openings is more, promote alkali-wash waste water and external source lye being uniformly distributed in neutralization reactor 2;This
Outside, acidic hydrolysis liquid matches liquid, the perforated area of the distributing device 23 via above-mentioned ring-like distributing device 23 in neutralization reactor 2
Small, cloth material mouth quantity is few, internal diameter is small, forms local turbulence after liquid out, facilitates the mass transfer between acidic hydrolysis liquid and lye
And neutralization reaction.
3, flocculation sedimentation system
Flocculation sedimentation system is used to for neutralizer and flocculant that neutralization reaction generates being sufficiently mixed and implements sedimentation separation;
The specific structure of flocculation sedimentation system is not limited strictly, the structure of this field routine can be used.
Specifically, flocculation sedimentation system includes the pipe-line mixer 8 and flocculation deposition apparatus 3 set gradually;Such as Figure 10 institute
Show, flocculation deposition apparatus 3 includes seal casinghousing 31, and annular overflow weir 32, central tube 33 and cloth are equipped with inside seal casinghousing 31
Expects pipe 34, the inside of the centrally disposed pipe 33 of cloth tube 34 are equipped with umbellate form baffle 35 in the bottom of central tube 33, in seal casinghousing
31 top is equipped with exhaust outlet 36, is equipped with water outlet 37 and feed inlet 38, water outlet 37 and annular in the side wall of seal casinghousing 31
Overflow weir 32 is connected to, and feed inlet 38 is connected to cloth tube 34, is equipped with slag notch 39 in the bottom of seal casinghousing 31.
It is understood that the liquid outlet 28 of neutralization reactor 2 is connect with the import of pipe-line mixer 8 by the road, in
It is equipped with the connecting line of 2 liquid outlet 28 of reactor and 8 import of pipe-line mixer plus agent mouth, flocculating agent formulation tank 65 goes out agent
Metering pump 75 and pipeline of the mouth through stainless steel material are connect with agent mouth is added.In the present invention, pipe-line mixer 8 is easy to implement neutralization
Coming into full contact between liquid and flocculant;In addition, carried out plus agent using the metering pump 75 of stainless steel material, convenient for make flocculant with
The flocculating effect that neutralizer is accurately matched to be optimal.
Flocculation deposition apparatus 3 with above structure is the vertical sedimentation basin form of sealing;Neutralizer containing wadding body
It is sufficiently mixed with flocculant through pipe-line mixer 8, enters above-mentioned flocculation deposition apparatus 3 through gravity flow and carry out precipitation and separation, concentration wadding
The moisture content of body reduces, and alleviates the processing load of subsequent mechanical dehydration device 4, while the strong brine of Precipitation can be back to
Hydrolysis reactor 1.Since the material in flocculation deposition apparatus 3 is possible to evolution gaseous pollutant, seal form is used, together
Gas is led to strong brine storage tank 62 and carries out water seal by the exhaust outlet 36 being arranged at the top of Shi Qi.In particular, based on separation equipment
Maturity and operational simplicity carry out strong brine and wadding using the flocculation deposition apparatus 3 of above-mentioned vertical sedimentation basin form
The separation of body;Neutralizer through feed inlet 38 enters flocculation deposition apparatus 3 after mixing with flocculant, and cloth tube 34 is downward by neutralizer
Central tube 33 is squeezed into, through 35 baffling of umbellate form baffle, metal hydroxides wadding body is concentrated to the bottom precipitation of flocculation deposition apparatus 3;
Meanwhile strong brine enters strong brine to the top lift of flocculation deposition apparatus 3, and through annular overflow weir 32 and the gravity flow of water outlet 37
Storage tank 62.When reaching certain sedimentation time, the interface being concentrated between wadding body and strong brine is clear, and strong brine is pressed from both sides almost without wadding body
Band.
4, mechanical dehydration device
Mechanical dehydration device 4 is used to be carried out dehydrating concentration wadding body, to significantly reduce solid slag amount;It wads a quilt with cotton in view of concentration
The solid content of body is about 2-3wt%, and contains strong brine, therefore it is defeated that the screw pump 78 of stainless steel material can be selected to carry out
It send.In addition, the moisture in concentration wadding body is based on Free water, therefore using conventional plate and frame filter press or centrifugal dehydrator
Obtain good dehydrating effect.Have the shortcomings that land occupation is big, the processing time is long in view of plate and frame filter press, cannot operate continuously, because
This mechanical dehydration device 4 is preferably centrifugal dehydrator, and separation factor can be 3000 or so, at this time can be by the wadding body system of concentration
The standby wet solid slag for being 60-70% at moisture content.
5, desiccation apparatus
Desiccation apparatus 5 is for being dried the wet solid slag formed through mechanical dehydration processing, to continue to reduce solid
Slag yield, and it is conducive to reuse.Wherein it is possible to be conveyed using screw conveyor 9 to wet solid slag;The mode of movement is more clear
It is clean, avoid belt transmission it is scaling-off phenomena such as.
Moisture in above-mentioned wet solid slag is mainly capillary water, no matter is difficult to using plate compression or centrifugal dehydration mode
Continue to reduce its moisture content and solid slag yield, carries out dehumidifying desiccation using drying mode and be more suitable for.Therefore, desiccation apparatus 5 can
To use thin layer desiccation machine or low temperature dehumidification desiccation machine, wet solid slag can be dried to the solid slag for moisture content 10-20%.
Thin layer desiccation machine has coupled conduction and radiant drying principle, hot fluid indirect heating manner is generally used, to wet
The vaporization rate of moisture is fast in solid slag, however energy consumption and equipment investment are higher;Low temperature dehumidification desiccation machine is former based on convective drying
Reason generally directly heats mode using electricity, and the speed for dehumidifying of gasifying is slower than thin layer drying, however equipment investment is low, technique behaviour
Make simple.In the case where can use there are waste heat medium (such as steam), it is preferred to use thin layer desiccation machine.Due in solid slag
Moisture be mainly the crystallization water, continue to reduce moisture content not only low efficiency and uneconomical.
In addition, the moisture in wet solid slag can be converted into water vapour during removal moisture drying, recycles vapour latent heat and return
It uses drying process and is more advantageous to reduction energy consumption.Therefore, system of the invention can also include heat reclaim unit (i.e. condensed water
Storage tank 6666), it is used to recycle the condensed water that above-mentioned desiccation apparatus 5 generates;Due to recycling the pollutional load of obtained condensed water
It is low, therefore the preparation of external source lye and flocculant can be back to.
6, other matching components
It is understood that system of the invention is other than including aforementioned body component, it further include other matching components,
Match including dead catalyst storage tank 61, strong brine storage tank 62, alkali-wash waste water storage tank 63, external source Alkali liquid compounding tank 64, flocculant
Tank 65 processed, condensation water storage tank 66, sump oil storage tank 67 and it is above-mentioned refer to it is various for conveying pump and conveyer of material etc.,
Can the conventional equipment or component of this field be used, and can be configured in a usual manner.
Specifically, dead catalyst storage tank 61 includes tank body, side-feeding mixer is equipped in tank interior, under tank wall
End is equipped with inlet port and outlet port, is equipped with evacuation port in tank base, is equipped with gas feed 611 in top of the tank;Wherein, side into
Formula blender is used to carry out the dead catalyst from different periods homogeneous average, and gas feed 611 is used to store up dead catalyst
The tank deck inflated with nitrogen of tank 61 is protected, and to avoid the contact with moisture in dead catalyst and air, prevents hydrolysis from exploding.
Strong brine storage tank 62 includes tank body and water sealing (sealing water) pipe, water inlet is equipped in tank wall upper end, in tank wall lower end
Equipped with water outlet, it is equipped with evacuation port in tank base, is equipped with water seal mouth in top of the tank, water sealing (sealing water) pipe is connect with water seal mouth.Setting
Strong brine storage tank 62 not only provided space for the storage of intermediate product strong brine, but also provided raw material for hydrolysis, was entire
The key node that system intermediate product recycles;Meanwhile by water seal can also control hydrolysis reactor, neutralization reactor with
And in flocculation deposition apparatus gaseous pollutant evolution, avoid air pollution.
Alkali-wash waste water storage tank 63 includes tank body, is equipped with side-feeding mixer in tank interior, is equipped in tank wall lower end
Water inlet and water outlet are equipped with evacuation port in tank base;Wherein, side-feeding mixer is used for the alkali cleaning from different periods
Waste water carries out homogeneous average.
Condensing water storage tank 66 includes tank body, is equipped with water inlet in tank wall upper end, is equipped with condensation in tank wall lower end
Water out is equipped with evacuation port in tank base.Storage of the condensation water storage tank 66 both for intermediate product condensed water is set, space is provided,
The preparation for external source lye and flocculant provides water source again, is the important node that whole system intermediate product recycles.
Further, dead catalyst storage tank 61 is connect by Machinery Diaphragm Pump 71 with the feed inlet 19 of hydrolysis reactor 1, dense
Brine reservoir 62 is connect by centrifugal pump 72 with the water inlet 18 of hydrolysis reactor 1, the oil discharge outlet 17 and sump oil of hydrolysis reactor 1
Storage tank 67 connects.
Further, the liquid outlet 110 of hydrolysis reactor 1 is connected by the inlet 27 of centrifugal pump 77 and neutralization reactor 2
It connects, alkali-wash waste water storage tank 63 and external source Alkali liquid compounding tank 64 pass through the alkali inlet 26 of metering pump 73,74 and neutralization reactor 2 respectively
Connection, the liquid outlet 28 of neutralization reactor 2 are connect with the import of pipe-line mixer 8.
Further, the outlet of pipe-line mixer 8 is connect with the feed inlet 38 of flocculation deposition apparatus 3, flocculation deposition apparatus 3
Slag notch 39 connect with the import of mechanical dehydration device 4 by screw pump 78.
Further, the slag-drip opening of mechanical dehydration device 4 is connect with feed bin 10;Feed bin 10 is by screw conveyor 9 and does
5 import connection is set in makeup;In addition, condensation water storage tank 66 is connect with desiccation apparatus 5 to recycle condensed water.Condense water storage tank 66 also
It is connect by metering pump 76 with the water inlet of the water inlet of external source Alkali liquid compounding tank 64 and flocculating agent formulation tank 65.
In particular, the water outlet of the exhaust outlet 25, flocculation deposition apparatus of the exhaust outlet 16 of hydrolysis reactor 1, neutralization reactor 2
Mouth 37 and exhaust outlet 36 are connect by pipeline with the water seal mouth of strong brine storage tank 62 respectively.
In addition, flocculation deposition apparatus 3 and mechanical dehydration device 4 have brine outlet, brine outlet and strong brine are stored up
Tank 62 connects, consequently facilitating carrying out reuse to strong brine.
System of the invention realizes the nothing of dead catalyst and alkali-wash waste water using hydrolysis reactor 1 and neutralization reactor 2
Evilization and oils resource reclaim, and realize metal using flocculation sedimentation system, mechanical dehydration device 4 and desiccation apparatus 5 and consolidate
The minimizing and recycling of slag;In addition, realizing the circulation benefit of intermediate product using strong brine storage tank 62 and condensation water storage tank 66
With.The operational process of whole system is mild, safe operation process, no new pollution source, high to the rate of recovery of resource, especially returns
The content for receiving the obtained molten W/O of acid and impurity is low, and the quality of oil product is high.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement;And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (18)
1. a kind of method for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, which is characterized in that including walking as follows
It is rapid:
1) chlorine aluminium acidic ionic liquids dead catalyst is mixed with strong brine and carries out hydrolysis, until chlorine aluminium acidic ionic liquids are useless
The residual activity of catalyst completely eliminates, and separates to hydrolysis product, respectively obtains acidic hydrolysis liquid and the molten oil of acid;
2) the acidic hydrolysis liquid is mixed with the lye comprising alkaline waste water and carries out neutralization reaction, until reaction system is weak base
Property, obtain the neutralizer containing metal hydroxides wadding body;
3) neutralizer and flocculant are sufficiently mixed and are implemented sedimentation separation, the strong brine for collecting upper layer is back to the water
Solution reaction, while collecting the concentration wadding body of lower layer;
4) the concentration wadding body is carried out dehydrating, collects wet solid slag, and the strong brine of abjection is back to the hydrolysis instead
It answers;
5) the wet solid slag is dried, obtains desiccation solid slag.
2. the method according to claim 1, wherein the content of sodium chloride is in the strong brine in step 1)
The input material volume ratio of 15-22wt%, the chlorine aluminium acidic ionic liquids dead catalyst and strong brine is 1:(50-60).
3. method according to claim 1 or 2, which is characterized in that in step 1), the hydrolysis is filled in plug flow
It is carried out in bed reactor, structured packing is filled in the plug flow packed bed reactor.
4. according to the method described in claim 3, it is characterized in that, the porosity of the structured packing is 0.95-0.97m3/m3,
Specific surface area is 300-500m2/m3;The air speed of the plug flow packed bed reactor is 0.25-0.5h-1。
5. according to the method described in claim 3, it is characterized in that, the structured packing is the orifice plate structured packing of Y type ripple;Institute
The material for stating structured packing is polyethylene, polyvinyl chloride or Kynoar.
6. the method according to claim 1, wherein the neutralization reaction is in complete mixing flow reactor in step 2)
Middle progress, the air speed of the complete mixing flow reactor are 1-2h-1。
7. method according to claim 1 or 6, which is characterized in that in step 2), the pH value of the neutralizer is 8.0-
8.5, and the content of metal hydroxides wadding body is 2.5-3% in neutralizer.
8. the method according to claim 1, wherein the flocculant is anionic polypropylene in step 3)
Amide, the relative molecular weight of the anion-polyacrylamide are 600-1800 ten thousand, charge density 10-40%.
9. according to the method described in claim 8, it is characterized in that, the dosage of the flocculant is that wadding is added in neutralizer per ton
Solidifying agent 20-30g, the time of the sedimentation separation are 2-3 hours.
10. the method according to claim 1, wherein the chlorine aluminium acidic ionic liquids dead catalyst is to utilize
The ionic liquid-catalyzed carbon four of chlorine aluminic acid class produces the dead catalyst that alkylate oil generates;The alkaline waste water is to utilize chlorine aluminic acid class
Ionic liquid-catalyzed carbon four produces the alkali-wash waste water that alkylate oil generates.
11. a kind of for implementing the system of any the method for claims 1 to 10 10, which is characterized in that including hydrolysis reactor,
Neutralization reactor, flocculation sedimentation system, mechanical dehydration device and desiccation apparatus;
The hydrolysis reactor, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis;
The neutralization reactor is connect with the hydrolysis reactor, the acidic hydrolysis liquid for generating the hydrolysis and packet
Lye mixing containing alkaline waste water carries out neutralization reaction;
The flocculation sedimentation system is connect with the neutralization reactor, neutralizer and flocculation for generating the neutralization reaction
Agent is sufficiently mixed and implements sedimentation separation;
The mechanical dehydration device is connect with the flocculation sedimentation system, for the concentration wadding body formed through the sedimentation separation
It is carried out dehydrating;
The desiccation apparatus is connect with the mechanical dehydration device, for doing to the wet solid slag formed through the dehydration
Dry processing.
12. system according to claim 11, which is characterized in that the hydrolysis reactor includes shell, in the shell
Top be successively arranged annular collection tank, the water distributor for being distributed strong brine from top to bottom and for being distributed chlorine aluminium acidic ionic
The distributing device of liquid dead catalyst is equipped with the filler support bracket for supporting filler in the lower part of the shell, in the shell
Top be equipped with exhaust outlet, be equipped with oil discharge outlet, water inlet and feed inlet, the oil discharge outlet and the ring in the side wall of the shell
The connection of shape collection tank, the water inlet are connected to the water distributor, and the feed inlet is connected to the distributing device, in the shell
Bottom be equipped with liquid outlet.
13. system according to claim 11, which is characterized in that the neutralization reactor is complete mixing flow reactor;It is described
Neutralization reactor includes shell, is successively arranged the water distributor for being distributed lye from top to bottom on the top of the shell and is used for
It is distributed the distributing device of neutralizer, is equipped with side-feeding mixer at the middle part of the shell, is equipped with exhaust at the top of the shell
Mouthful, be equipped with alkali inlet and inlet in the side wall of the shell, the alkali inlet is connected to the water distributor, the inlet and
The distributing device connection is equipped with liquid outlet in the bottom of the shell.
14. system according to claim 12 or 13, which is characterized in that the water distributor includes cloth supply mains, described
The two sides of cloth supply mains are respectively equipped with multiple parallel and spaced set water distribution branch pipes, are distributed in the bottom of each water distribution branch pipe
There are multiple water distributing pores, the total open area of water distributing pore accounts for 1% or more of reactor cross section product.
15. system according to claim 12 or 13, which is characterized in that the distributing device includes cloth general pipeline, described
The two sides of cloth general pipeline are respectively equipped with multiple concentric and spaced set semicircle cloth branch pipes, in each semicircle cloth branch
Multiple cloth holes are distributed in the bottom of pipe, and the total open area in cloth hole accounts for 2% or more of reactor cross section product.
16. system according to claim 11, which is characterized in that the flocculation sedimentation system includes the pipeline set gradually
Mixer and flocculation deposition apparatus, the flocculation deposition apparatus include seal casinghousing, and annular is equipped with inside the seal casinghousing
The inside of the central tube is arranged in overflow weir, central tube and cloth tube, the cloth tube, is equipped in the bottom of the central tube
Umbellate form baffle is equipped with exhaust outlet at the top of the seal casinghousing, is equipped with water outlet and charging in the side wall of the seal casinghousing
Mouthful, the water outlet is connected to the annular overflow weir, and the feed inlet is connected to the cloth tube, in the seal casinghousing
Bottom is equipped with slag notch.
17. system described in 2,13 or 16 according to claim 1, which is characterized in that further include strong brine storage tank, in the dense salt
The top of water storage tank is equipped with water seal mouth, and the exhaust outlet is connect by pipeline with the water seal mouth of the strong brine storage tank.
18. system according to claim 11, which is characterized in that the desiccation apparatus is thin layer desiccation machine or low temperature dehumidification
Desiccation machine.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810172039.XA CN109200978B (en) | 2018-03-01 | 2018-03-01 | Method and system for treating waste catalyst of chloroaluminate ionic liquid and alkaline wastewater |
CA3092413A CA3092413C (en) | 2018-03-01 | 2018-12-24 | Method and system for treatment of spent chloroaluminate ionic liquid catalyst and alkaline wastewater |
PCT/CN2018/123215 WO2019165834A1 (en) | 2018-03-01 | 2018-12-24 | Method and system for treatment of spent chloroaluminate ionic liquid catalyst and alkaline wastewater |
CN201880090315.6A CN111770791B (en) | 2018-03-01 | 2018-12-24 | Method and system for treating chloroaluminate ionic liquid waste catalyst and alkaline wastewater |
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Cited By (4)
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CN110646272A (en) * | 2019-09-26 | 2020-01-03 | 武汉海关技术中心 | Method for purifying hydrophilic ionic liquid |
CN112499844A (en) * | 2019-09-16 | 2021-03-16 | 中国石化工程建设有限公司 | System and method for treating waste ionic liquid |
CN115849402A (en) * | 2021-09-23 | 2023-03-28 | 中国石油化工股份有限公司 | Treatment method and treatment system for waste chloroaluminate ionic liquid catalyst |
CN117566882A (en) * | 2024-01-16 | 2024-02-20 | 新乡化纤股份有限公司 | Method for removing impurities in ionic liquid aqueous solution |
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CN109200978B (en) * | 2018-03-01 | 2023-06-06 | 中国石油大学(北京) | Method and system for treating waste catalyst of chloroaluminate ionic liquid and alkaline wastewater |
CN115869579B (en) * | 2021-09-29 | 2024-06-04 | 中国石油化工股份有限公司 | Method and device for solidifying waste chloroaluminate ionic liquid |
CN113830869B (en) * | 2021-09-30 | 2024-01-30 | 中国华能集团清洁能源技术研究院有限公司 | Baffling type gas-liquid reaction system for treating concentrated alkali liquor and working method thereof |
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CA3092413C (en) | 2022-05-24 |
CA3092413A1 (en) | 2019-09-06 |
US20200392029A1 (en) | 2020-12-17 |
CN111770791A (en) | 2020-10-13 |
CN109200978B (en) | 2023-06-06 |
US11426702B2 (en) | 2022-08-30 |
CN111770791B (en) | 2022-02-18 |
WO2019165834A1 (en) | 2019-09-06 |
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